WO2002006045A1 - Film metallise a base de polypropylene a orientation biaxe, destine a l'emballage - Google Patents

Film metallise a base de polypropylene a orientation biaxe, destine a l'emballage Download PDF

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Publication number
WO2002006045A1
WO2002006045A1 PCT/US2001/022079 US0122079W WO0206045A1 WO 2002006045 A1 WO2002006045 A1 WO 2002006045A1 US 0122079 W US0122079 W US 0122079W WO 0206045 A1 WO0206045 A1 WO 0206045A1
Authority
WO
WIPO (PCT)
Prior art keywords
laminate film
layer
astm
resin layer
polymer
Prior art date
Application number
PCT/US2001/022079
Other languages
English (en)
Inventor
Keunsuk P. Chang
Mark S. Lee
Leo R. Moreau
Original Assignee
Toray Plastics (America), Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US09/715,013 external-priority patent/US6916526B1/en
Application filed by Toray Plastics (America), Inc. filed Critical Toray Plastics (America), Inc.
Priority to AU2002222919A priority Critical patent/AU2002222919A1/en
Publication of WO2002006045A1 publication Critical patent/WO2002006045A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • B32B2038/0028—Stretching, elongating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2310/00—Treatment by energy or chemical effects
    • B32B2310/14—Corona, ionisation, electrical discharge, plasma treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B32B2323/10—Polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation

Definitions

  • This invention relates to a metallized polypropylene film containing a metal adhesion layer comprising a polymer wax and a polyolefin resin.
  • a polyethylene wax is blended with a polypropylene resin.
  • Biaxially oriented polypropylene metallized films are used for many packaging applications, particularly in food packaging, because they have important sealing and protective qualities.
  • the films minimize the amount of light, moisture, and oxygen which can normally enter an ordinary, unprotected package.
  • the films are often used in food packaging in combination with gas-flushing applications to protect the contents from moisture and oxidation. Also, the films often provide a heat sealable inner layer for bag forming and sealing.
  • Metallized films used in vertical-form-fill-seal (VFFS) packaging provides an excellent barrier in both unlaminated or laminated forms.
  • VFFS vertical-form-fill-seal
  • the laminated packaging containing the metallized film can be stretched in the packaging machine from 5 to 10% beyond the dimensions of the original film packaging. This stretching may cause fracture or cracks to form in the metal layer of the film.
  • the packaging loses its protective properties. For instance, oxygen can readily pass through a damaged packaging film and cause unwanted oxidation of the contents.
  • U.S. Patent No. 5,698,317 which is incorporated herein by reference, discloses the use of a four layer packaging film having a polyolefin resin layer sandwiched between a polyolefin resin layer comprising a petroleum or terpene resin and a heat sealable layer or non-sealable winding layer. A metal layer is then deposited on the surface of the polyolefin resin layer. The metal layer is deposited following the discharge treatment of the polyolefin resin layer.
  • the present invention improves upon the moisture and gas barrier properties as well as the durability of the metal layer. Summary of the Invention
  • the invention helps solve the problem of leaky bags associated with conventional metallized film packaging and the bag- forming process by providing an improved polyolefin resin layer.
  • the improved resin layer comprises a polymer resin with a polymer additive to form a resin layer.
  • the addition of the polymer additive to the polymer resin enhances the adhesion between the blended polymer resin layer and the metal layer, and thus improves upon the durability of the packaging film during the bag forming process.
  • the invention provides a metallized, laminate film which exhibits little or no fracture or cracking during the bag-forming process.
  • the enhanced adhesive properties of the invention also improves upon the moisture and gas barrier properties of laminate film.
  • One embodiment of this invention is a laminate film comprising a polymer core layer; a resin layer disposed on a surface of said polymer layer; and a metal layer deposited on a surface of said resin layer; wherein the laminate film has metal adhesion of 2 or more; and wherein the laminate film has O 2 TR of 100 cc/m 2 /day or less at 38°C and 0% relative humidity as measured on a 15 ⁇ m laminate film elongated 9% in the machine direction.
  • Another embodiment is a laminate film comprising a polymer core layer; a resin layer disposed on a surface of said polymer layer; a metal layer deposited on a surface of said resin layer; and means for enhancing adhesion between the resin layer and the metal layer.
  • the means for enhancing adhesion could be an additive, which is polymeric or non- polymeric, organic or inorganic.
  • Another embodiment of this invention is a method of manufacturing a laminate film, comprising extruding a polymer core layer; extruding a resin layer disposed on a surface of said polymer layer; and extruding a metal layer deposited on a surface of said resin layer; the laminate film having metal adhesion of 2 or more; and the laminate film having O 2 TR of 100 cc/m 2 /day or less at 38°C and 0% relative humidity as measured on a 15 ⁇ m laminate film elongated 9% in the machine direction.
  • One embodiment of this invention is a method for food packaging, comprising obtaining a laminate film and covering food with the laminate film; the laminate film comprising a polymer core layer; a resin layer disposed on a surface of said polymer layer; and a metal layer deposited on a surface of said resin layer; wherein the laminate film has metal adhesion of 2 or more; and wherein the laminate film has O 2 TR of 100 cc/m 2 /day or less at 38°C and 0% relative humidity as measured on a 15 ⁇ m laminate film elongated 9% in the machine direction.
  • the invention is of a laminate film comprising: a polyolefin resin layer; a polymer core layer; a heat sealable layer or non-sealable winding layer formed on the surface of a polymer core layer opposite the polyolefin resin layer; and a metal layer disposed on the polyolefin resin layer.
  • the polymer core layer is sandwiched between the resin layer and the heat sealable layer.
  • the invention contains a polyolefin resin layer having about 1 to 30 percent by weight, preferably 1 to 20 percent by weight, more preferably 1 to 10 percent by weight of a polymer additive.
  • the polymer additive is selected from a group of synthetic polymer waxes. In the preferred embodiment a polyethylene crystalline wax is added to a polypropylene resin.
  • the polyolefin resin layer may optionally contain up to 1000 ppm of antiblock additives such as silicas, aluminosilicates, or metal-aluminosilicates.
  • the heat sealable layer or non-sealable winding layer may also contain antiblock components such as silicas, aluminosilicates, or polymeric antiblocks such as crosslinked silicone polymer in the amount of 0.10 - 0.50% by weight of the heat sealable or non-sealable winding layer. It is also preferred that the surface of the polyolefin resin layer be corona discharged treated to give excellent printability and promote adhesion between the resin layer and the metal layer.
  • the metal layer is preferably a vapor deposited metal, preferably vapor deposited aluminum.
  • the laminate film comprises four layers.
  • a polymer core preferably a polypropylene core
  • a polyolefin resin layer with at least one component selected from the family of synthetic polymer waxes, preferably a crystalline, polyethylene wax, and a heat sealable surface or a winding surface.
  • the heat sealable layer will contain an antiblock and/or slip additives for good machinability and a low coefficient of friction.
  • the resin layer is then discharge treated.
  • Al metal is then vapor-deposited upon the discharge treated resin layer.
  • the heat sealable layer is used as a winding surface, its surface may also be discharge treated to make it suitable for laminating or converter applied adhesives and inks.
  • the laminate film of the invention comprises the following material components, and is made according to the following procedure.
  • a propylene polymer resin and a polyethylene wax having a molecular weight of about 3000, a viscosity of about 110 cp at 149°C, and a melting point of about 129 °C are blended together.
  • a crystalline, propylene polymer resin is blended with a crystalline, linear, polyethylene wax.
  • an antiblock additive preferably sodium calcium aluminosilicate powder having a mean particle diameter of about 3 ⁇ m is added to the polymer blend. The mixture is then extruded to form a polyolefin resin layer with a thickness of 0.75 ⁇ m.
  • the polyolefin resin layer is coextruded with a polymer core layer, preferably a polypropylene core layer, having a thickness between 5 and 36 ⁇ m, preferably between 10 and 20 ⁇ m, and more preferably between 10 and 15 ⁇ m, and a heat sealable layer opposite the resin layer having a thickness between 0.5 and 5 ⁇ m, preferably between 0.6 and 3.0 ⁇ m, and more preferably between 0.8 and 2.0 ⁇ m.
  • the coextrusion process includes a three-layered composite die.
  • the polymer core layer is sandwiched between the polyolefin resin layer and the heat sealable layer.
  • the three layer laminate sheet is cast onto a cooling drum whose surface temperature is controlled between 20 °C and 60 °C to solidify the non- oriented laminate sheet.
  • the non-oriented laminate sheet is stretched in the longitudinal direction at about 135 to 165 °C at a stretching ratio of about 4 to about 5 times the original length and the resulting stretch sheet is cooled to about 15 °C to 50 °C to obtain a uniaxially oriented laminate sheet.
  • the uniaxially oriented laminate sheet is introduced into a tenter and preliminarily heated between 130 °C and 180 °C, and stretched in the transverse direction at a stretching ratio of about 7 to about 12 times the original length and then heat set to give a biaxially orientated sheet.
  • the biaxially oriented film has a total thickness between 6 and 40 ⁇ m, preferably between 10 and 20 ⁇ m, and most preferably between 12 and 18 ⁇ m.
  • the surface of the polyolefin resin layer of the biaxially oriented laminate film is subjected to
  • crystalline linear polyethylene wax having a molecular weight of 400 - 3000, a melting point of 80 - 132 °C by ASTM D127, a viscosity of 149 °C of 2 - 170 cp by ASTM D3236 or a viscosity at 99 °C of 40 - 60 SSU by ASTM D88, needle penetration at 25 °C of 15 - 0.0 dmm by ASTM D1321, and density at 25 °C of 0.92 - 0.99 by ASTM D1298.
  • the additive material consists of a synthetic branched ethylene copolymer wax, having a molecular weight of 500 - 3000, a melting point of 90 - 120 °C by ASTM D127, a viscosity at 99 °C of 58 - 120 SSU by ASTM D 88, needle penetration at 25 °C of 13.0 - 2.0 dmm by ASTM 1321, and average branches per molecule of 0.5 - 4.0.
  • the additive material consists of a synthetic hydroxyl- terminated polyethylene wax, having a molecular weight of 375 - 700, a melting point of 78 - 105 °C by ASTM D127, a viscosity at 149 °C of 2.0 - 10.0 cp by ASTM D3236, needle penetration at 25 °C of 10.0 - 1.5 dmm by ASTM 1321, density at 25 °C of 0.95 - 0.96 by ASTM D792, and hydroxyl number of 127 - 65 mg KOH/g by ASTM D222.
  • the additive material is a synthetic carboxyl-terminated polyethylene wax, having a molecular weight of 390 - 715, a melting point of 89 - 110 °C by ASTM
  • this layer will comprise a ternary ethylene-propylene-butene copolymer.
  • this layer will comprise a crystalline polypropylene or a matte layer of a block copolymer blend of polypropylene and one or more other polymers whose surface is roughened during the film formation step so as to matte the winding layer.
  • the surface of the winding layer is discharge-treated to provide a functional surface for lamination or coating with adhesives and/or inks.
  • the discharge treatment of said polyolefm-based resin layer is typically performed in an atmosphere of CO 2 and/or N 2 .
  • the laminate film of the invention will have a thickness of about 6 to 40 ⁇ m thick.
  • the polyolefin resin layer will have a thickness of about 0.2 to 5.0 ⁇ m.
  • the heat-sealable layer or non-heat-sealable winding layer will have a thickness of 0.5 to 5.0 um, and contains an anti-blocking agent of about 0.05 - 0.5%) by weight of the heat-sealable layer.
  • the vapor deposited metal layer, preferably an aluminum layer, formed on the discharge- treated surface of the polyolefin-based resin layer has a thickness of 5 to 70 nm. Test Methods
  • Oxtran 2/20 unit substantially in accordance with ASTM D3985.
  • the preferred value was an average value equal to or less than 15.5 cc/m 2 /day with a maximum of 46.5 cc/m 2 /day.
  • B) "Moisture transmission rate" of the film was measured by using a Mocon
  • Permatran 3/31 unit measured substantially in accordance with ASTM F1249. In general, the preferred value was an average value equal to or less than 0.155 g/m 2 /day with a maximum of 0.69 g/m 2 /day.
  • Optical density was measured using a Tobias Associates model TBX transmission densitometer. Optical density is defined as the amount of light reflected from the test specimen under specific conditions. Optical density is reported in terms of a logarithmic conversion. For example, a density of 0.00 indicates that 100% of the light falling on the sample is being reflected. A density of 1.00 indicates that 10% of the light is being reflected; 2.00 is equivalent to 1%, etc.
  • Method adhesion was measured by adhering a strip of 1-inch wide 610 tape to the metallized surface of a single sheet of metallized film and removing the tape from the metallized surface. The amount of metal removed was rated qualitatively as follows:
  • O 2 TR oxygen transmission rate
  • MVTR moisture vapor transmission rate
  • One hundred parts by weight of a crystalline propylene homopolymer resin 5 parts by weight of a crystalline linear polyethylene wax having a molecular weight of 3000, a viscosity of 110 cp at 149°C, and a melting point of 129°C; and 0.00015 parts by weight of a sodium calcium aluminosilicate powder having a mean particle diameter of 3 ⁇ m, were blended together. The mixture was then extruded to form a polyolefin resin layer with a thickness 0.75 ⁇ m.
  • the polyolefin resin layer is coextruded with a propylene homopolymer core layer having a thickness 13.25 ⁇ m, and a heat sealable layer opposite the resin layer having a thickness 1.0 ⁇ m.
  • the three layer film is coextruded so as to from a biaxially oriented film with a total thickness of 15 ⁇ m.
  • the film was then discharge- treated on the polyolefin resin layer side (the metallizing surface) and wound in roll form.
  • the roll was then placed in a metallizing chamber and aluminum was vapor-deposited on the discharge-treated polyolefin resin layer surface.
  • the metallized film was then tested for oxygen and moisture permeability, optical density, metal adhesion, and barrier durability.
  • Example 2 A process similar to that of Example 1 was repeated except that 10 parts by weight of the crystalline linear polyethylene wax of molecular weight was used.
  • Example 2 A process similar to that of Example 1 was repeated except that a branched, ethylene, copolymer wax of having a molecular weight of 1200, a viscosity of 88 SSU at 99°C, and a melting point of 112°C was substituted for the linear polyethylene wax.
  • Example 2 A process similar to that of Example 1 was repeated except that no crystalline linear polyethylene wax was used in the polyolefin resin layer.
  • Comparative Example 2 A process similar to that of Example 1 was repeated except that 12.5% by weight of a polydicyclopentadiene petroleum resin was used in place of the crystalline linear polyethylene wax in the polyolefin resin layer.
  • the overall total thickness of the oriented film was increased to 17.5 ⁇ m instead of 15 ⁇ m by increasing the accompanying coextruded propylene homopolymer core layer to 15.25 ⁇ m and the heat sealable layer to 1.5 ⁇ m.
  • the polyolefin resin layer thickness remained at 0.75 ⁇ m.
  • Table 1 shows that the metal adhesion of the laminate films of Examples 1-3 is considerably superior to that of Comparative Examples 1 and 2.
  • Figure 1 shows that the barrier durability as measured by O TR of the laminate film of Example 1 is far better than that of Comparative Example 1.
  • Figure 1 also shows that the barrier durability of the laminate film of Example 1 having a film thickness of 15 ⁇ m is better than or comparable to the laminate film of Comparative Example 2 having a film thickness of 17.5 ⁇ m.
  • the O 2 TR value is inversely proportional to the square of the thickness.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un film stratifié comprenant une couche de base polymère, une couche de résine déposée sur une surface de la couche polymère, ainsi qu'un métal déposé sur une surface de la couche de résine. Le film stratifié ainsi obtenu possède une excellente adhésion entre la couche de résine et la couche de métal, ainsi qu'une durabilité en tant que barrière.
PCT/US2001/022079 2000-07-13 2001-07-13 Film metallise a base de polypropylene a orientation biaxe, destine a l'emballage WO2002006045A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002222919A AU2002222919A1 (en) 2000-07-13 2001-07-13 Biaxially oriented polypropylene metallized film for packaging

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US21804400P 2000-07-13 2000-07-13
US60/218,044 2000-07-13
US22151000P 2000-07-28 2000-07-28
US60/221,510 2000-07-28
US09/715,013 US6916526B1 (en) 2000-07-19 2000-11-20 Biaxially oriented polypropylene metallized film for packaging
US09/715,013 2000-11-20

Publications (1)

Publication Number Publication Date
WO2002006045A1 true WO2002006045A1 (fr) 2002-01-24

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AU (1) AU2002222919A1 (fr)
WO (1) WO2002006045A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022264136A1 (fr) * 2021-06-14 2022-12-22 Melodea Ltd. Procédés de métallisation et produits formés à partir de ceux-ci

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4397916A (en) * 1980-02-29 1983-08-09 Mitsui Petrochemical Industries, Ltd. Laminated multilayer structure
US5717048A (en) * 1994-12-07 1998-02-10 Dai-Ichi Kogyo Seiyaku Co., Ltd. Cation-modified acrylamide or methacrylamide copolymer as well as antistatic agent, thermoplastic resin composition, aqueous composition and thermoplastic resin laminate comprising same
US6194061B1 (en) * 1998-05-25 2001-02-27 Toyo Boseki Kabushiki Kaisha Thermoplastic laminate film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4397916A (en) * 1980-02-29 1983-08-09 Mitsui Petrochemical Industries, Ltd. Laminated multilayer structure
US5717048A (en) * 1994-12-07 1998-02-10 Dai-Ichi Kogyo Seiyaku Co., Ltd. Cation-modified acrylamide or methacrylamide copolymer as well as antistatic agent, thermoplastic resin composition, aqueous composition and thermoplastic resin laminate comprising same
US5859141A (en) * 1994-12-07 1999-01-12 Dai-Ichi Kogyo Seiyaku Co., Ltd. Thermoplastic resin composition comprising cation-modified acrylamide or methacrylamide copolymer
US6194061B1 (en) * 1998-05-25 2001-02-27 Toyo Boseki Kabushiki Kaisha Thermoplastic laminate film

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022264136A1 (fr) * 2021-06-14 2022-12-22 Melodea Ltd. Procédés de métallisation et produits formés à partir de ceux-ci

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